Plastic compositions



ticizers therefor.

This case is a continuation in part of applica- Patented Nov. 12, l 935 2,021,121 v rmsrro COMPOSITIONS Harry Ben Dykstra, Wilmington, Del., and Walter Eastby Lawson, -Woodbury, N. J., assignors to E. I. du Pont -de Nemours & Company, Wilmington, Del., a corporation oi Delaware 10o Drawing. Application April 8, 1934, Serial No.

719,292. In Great Britain February 19, 1931 9Claims.

This invention relates to new compositions of matter, more particularly to plastic compositions, and specifically to plastic compositions comprising organic plastic substances and plastion .Serial No. 395,739, filed September 2'7, 1929.

This invention has as an object the preparation of plastic compositions comprising organic plastic substances and as plasticizers therefor esters of dibasic acids, said dibasic acids being derivable by the action of dibasic acids on hydroxy carcellulose derivatives and esters of the above described, acids. A still further object is the preparation of the esters themselves.

will appear hereinafter.

These objects are accomplished by the following invention, wherein an ester of a dicarboxylic acid such as phthalyl glycollic acid is prepared and then used as a plasticizer-in the preparation of organic plastic compositions.

Other objects It has been found that esters of phthalylglycollic acid may be prepared by reacting esters of glycollic acid with phthalic anhydride followed by esterification of the remaining carboxyl group with another alcohol or another mol. of

These esters may also be prepared by reacting esters. of chloroacetic acid with alkali metal salts of alkyl acid phthalates. It has also been found that these esters and their analogs, as described below, are useful in the preparation of plastic compositions.

Having outlined above the general purposes of the invention, the following applications of the general principle thereof to certain specific instances are included for purposes of illustration and not in limitation.

glycollic ester.

Example 1 tough finishes.

Example 2 Butyl phthalyl vinyl glycollate.--A mixture containing 30 g. vinyl chloroacetate. 61 g. sodium butyl phthalate, and g. toluene was refluxed gently for 2 hours in an oil bath. The reaction mixture was washed with water, then the toluene layer was separated, dried and distilled until the temperature reached C. The mixture was filtered again and then distilled under reduced 10 pressure When a product boiling at 220 to 245 C. at 20 mm. pressure was obtained. This material was butyl phthalyl vinyl glycollate.

Example 3 15 Methoxyethyl phthalyl methyl glycollate.-A mixture containing 148 g. phthalic anhydride, 90 g. methyl glycollate, and 200 g. ethylene dichloride was heated at 100 for 9 hours. Seventyw six g. methoxyethanol and 2 g. sulfuric acid was then added and the mixture distilled in an apparatus designed to separate the water from the distillate, and return ethylene dichloride to the reaction vessel. After heating for 14 hours the 2g mixture was washed with water containing sodium carbonate to remove the sulfuric acid and unreacted phthalic acid. The product was refined by heating to 135 C. at 50 mm. pressure-to remove all volatile material. The product was 30 :hen treated with decolorizing carbon and illered.

Example 4 Methyl phthalyl methyl glyc0llate.--A mixture 35 containing 740 g. phthalic anhydride and 1000 g. methanol was refluxed until the acid number indicated the formation of methyl acid phthalate.

This material was neutralized by adding a soludistilled. The remaining product was washed with water and then heated to C. under 50 mm. vacuum to remove volatile materials. The 50 resulting product was treated with decolorizing carbon and filtered. The saponification number indicated that this material was substantially pure methyl phthalyl methyl glycollate. 55

Example 5 Cyclolt'exyl phthalyl cyclohexul glycollate- Two gram molecular weights of potassium cyclohexyl phthalate in 800 cc. of ethyl alcohol was treated with 2 gram molecular weights cyclohexyl chloroacetate and the mixture refluxed for 15 hours. This product was purified as described in Example 4.

' Example 6 Isobutyl phthalyl isobutyl glycollate-This product was prepared in the manner identical with that described in previous examples.

Other esters prepared by this same method include m'ethoxyethyl 'phthalyl methoxyethyl glycollate and propyl phthalyl propyl glycollate.

Example 8 Methyl alpha (methyl phthalyloxy) isobutyrate-Two gram molecular weights potassium methyl phthalate in methyl alcohol was treated with 2 gram molecular weights methyl alpha chloro-isobutyrate and the mixture refluxed for 40 hours. The resulting product was purified as described in previous examples.

In a similar manner esters of phthalyllactic acid may be prepared by using esters of alpha chloropropionic acid. Esters of phthalyllactic acid may likewise be prepared by a process similar to that of Example 3'from esters of lactic acid. Esters may likewise be prepared by reacting dipotassium phthalate with esters of chloroacetic acid esters but this method is not as satisfactory as the methods above described. Other esters for example, esters of adipyl glycollic acid may also be prepared, but these compounds, likewise,

are not as readily prepared as those above described because of the difliculty of making a pure half ester of adipic acid. Esters from polyhydric alcohols may be prepared. Thus, ethylene glycol di-mono-chloroacetate may be reacted with potassium butyl phthalate to give bis- (butyl phthalyl) glycol glycollate. The esters may be conveniently formulated as follows:

wherein R and R are monovalent radicals derived from an aliphatic, aromatic or cyclo-parafiinic alcohol. R and R thus include monovalent radicals derived from an aliphatic, aromatic, or cycloparaifinic ether alcohol. R is a divalent organic radical, and R a divalent aliphatic hydrocarbon radical. Thus, B may be butyl, methoxyethyl, methyl, cyclohexyl, lauryl, isobutyl, and propyl as disclosed in the above examples, as well as ethyl, benzyl, etc., It may be furnished by difew minutes.

hydroxy normal butyric and hydracrylic acids 5 may be employed. R may be furnished by various alcohols or alcohol derivatives such as vinyl, methyl, cyclohexyl, lauryl, isobutyl, propyl, methoxyethyl, tetrahydrofurfuryl, ethyl, benzyl, etc., alcohols, glycol, etc. These esters are disl0 closed and claimed in our copending application Serial No. 749,762, filed October 24, 1934.

The esters are substantially non-volatile and have been found to be satisfactory plasticizers for cellulose derivatives and natural and synl5 theti re of the type containing a plurality of ester /or ether linkages The resins with which these new plasticizing esters may be used include polymerized vinyl acetate, polymerized methyl methacrylic, polyhydric alcohol polybasic 20 acid resins, phenolaldehyde resins, modified phenol aldehyde resins, and many natural resins such as damar, pontianac, sandarac, -lrauri, shellac, etc., and their derivatives, e. 'g., ester gum hydrogenated rosin, and hydrogenated ester gum. 25

The above examples indicate that in general any alcohol may be used to esterify the chloroacetic acid or phthalic acid, or the equivalents of these.- Different alcohols may also be used for the formation of mixed esters.

Typical coating compositions containing these derivatives are given in the following examples:

Example 9 Parts Cellulose nitrate 12 Damar... 3 Lauryl phthalyl lauryl glycollate 4 Castor oil 2.6 Solvent 166 Example 10 Parts Polyvinyl ace 10 Bis-(ethyl phthalyl) glycol glycollate 3' Solvent Example 11 Parts Cellulose acetate 12' 50 Methyl phthalyl methyl glycollate 6 Solvent 182 Example 12 Parts 55 Cellulose nitrate 10 Resin 6 Butyl phthalyl butyl glycollate 6 Parafiin wax 2 Solvent 1'70 60 Example 13 Parts Polyhydric alcohol-polybasic acid resin 10 Methyl alpha (methyl phthalyloxy) isobutyrate 4 Solvent 50 The above lacquers give films which dry in a The films are flexible and very durable. By the term solvent in the above ex- '70 amples is meant a suitable mixture of esters, alcohols, and hydrocarbons such as is utilized in the art.

Typical plastic compositions containing these esters are given in the following examples: '7;

collate Example 15 Parts Cellulose nitrate 100 yclohexyl phthalyl cyclohexyi lactate 50 Pigment a 200 Example 16 Parts Ethyl cellulose 100. Lauryl phthalyl lauryl glycollate 15 Example 17 a Parts Polymerized methyl methacrylate 100 Isobutyl phthalyl isobutyl glycollate 20 Example 14 Parts Cellulose acetate 100 Methoxyethyl phthalyl methoxy ethyl gly- The above plastic compositions may be prepared with or without the usual volatile solvents, that is alcohol, acetone or mixtures of toluolalcohol, etc. Other cellulose derivatives, other natural resins, and other synthetic resins than those mentioned above may be employed, such as cellulose propionate, cellulose butyrate, cellulose isobutyrate," cellulose crotonate, cellulose acetobutyrate, benzyl cellulose, glycol cellulose, etc. Phenol-formaldehyde resins, polystyrene resins, ketone condensation products, ether resins, etc. may also be used. A part of the plasticizer in any of the above compositions may be replaced by'other plasticizers covered by this invention or by one or more of the plasticizers generally used for this purpose. Pigments and/or other modifying agents such as drying oils, semidrying oils and the like may also be employed.

It is to be noted that most of the organic plastic substances plasticized by the esters of the present invention have this in common, that they are highly polymeric materials, resinous or quasiresinous in nature. and having a plurality of C-O-'-C linkages either ,in the form-of ester linkages or ether linkages. While the cause for the plasticizing power is not as yet known, the

presence of a plurality of C-'OC"linkages in the material tobe plasticized and of a plurality of C-O-C linkages in the plasticizing material may have some bearing on the plasticizing property of the latter.

The derivatives of the present invention may be used in the preparation of various types of compositions containing cellulose derivatives and/or natural and synthetic resins, oils and filling materials. Thus, they may be used in the preparation of lacquers and enamels for coating metal, wood and paper,.in dopes for coating fabrics, in moisture-proof lacquers for coating regenerated cellulose, in plastic compositions to be used in the preparation of toilet-ware novelties,

sheeting. rods, tubes, safety-glass interlayers, etc., in lacquers for coating wire screens, and in the preparation of thin sheets for wrapping purposes.

The plasticizers of the present invention are of great utility because of their very high boiling point, and great water resistance. They are highly compatible with cellulose derivatives and the natural and synthetic resins described, and due to their low vapor pressure, give permanently flexible products.

The'above description and examples are intended to be illustrative only. Any modification of or variation therefrom which conforms to the spirit of the invention is intended to be included within the scope of the claims.

, We claim:

l. A composition of matter comprisingan organicplastic substance having a plurality of C-OC linkages of the class consisting of resins and cellulose derivatives, and as a plasticizer 20 therefor, an ester of the formula:

wherein R and R are monovalent radicals derived from monohydric alcohols, R. is a divalent 2 hydrocarbon radical, and R is a divalent aliphatic hydrocarbon radical.

2. A composition of matter comprising a cellui lose derivative, and as a plasticizer therefor, an

ester of the formula:

R -o-co R=-co o-a=-co-o rt* lose derivative, and as a plasticizer therefor, an

ester of phthalylglycollic acid.

5. A composition of matter comprising a cellulose derivative, and', as a plasticizer therefor, an alkyl ester of phthalyglycollic acid.

6. A composition of matter comprising a cellulose derivative, and as a plasticizer therefor, a vinyl ester of phthalylglycbllic acid. 7 5o 7. A composition of matter comprising a cellulose derivative, and as a plasticizer therefor, butyl phthalyl vinyl glycollate.

8. A composition of matter comprising a cellulose derivative, and as a plasticizer therefor, a 55 butyl ester of phthalylglycollic acid.

9. A composition of matter comprising a cellulose derivative, and as a plasticizer therefor, isobutyi phthalyl isobutyl glycollate.

- HARRY BEN DYKSTRA.

WALTER EABTBY LAWSON. 

